Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene

A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NO_x. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO₂ concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.     

含氮化合物的实验方法初步评价

对吡咯类含氮化合物的两种分离方法以及两步分离法中使用国产与进口试验的实验结果进行了对比与评价。结果表明,分离方法不同,所得吡咯类含氮化合物总体馏分的丰度也不同,一步分离法普遍低于两步法;不同分离方法对吡咯类化合物相对分布的影响较小。国产与进口试验性能不影响吡咯类含氮化合物的绝对丰度与相对分布的分析结果,两步分离法具备分析试剂国产化的条件。     

苏北盐城凹陷天然气与凝析油的成因机制

盐城凹陷天然气中甲烷含量高,碳同位素具有正分布系列,主体具有高成熟腐泥型气特征,伴随产出的凝析油则体现出与本区湖相原油和海相原油既相似又相区别的特征。不同组分间存在成熟度差异,轻质组分反映高成熟,中等组分体现出未熟低熟,重质组分表现出成熟特征。母源分析对比表明天然气与凝析油主要源自古生界海相腐泥型源岩,混有泰州组少许贡献,造成组分差异和成熟度变化的重要原因是大量气体注入配以长期发育断裂引起的运移分馏和不同成熟度油气混合所致。     

湖泊磷的核磁共振(NMR)分析——1环境标准样品的31P-NMR表征

通过对环境标准样进行31P-NMR测试,研究了磷的化学结构与化学位移的关系.结果表明:无机正磷酸盐(PO43-)化学位移在6.412×10-6,焦磷酸盐的化学位移在-4.353×10-6;多聚磷的化学位移分布特点是:主链末端磷化学位移在-3.53×10-6至-4.40×10-6之间,中间磷在-18.159×10-6至-20.246×10-6之间,有机磷中单酯和二醑的化学位移分别在4.3540×10-6至6.3652×10-6和-0.107×10-6至2.195×10-6之间,部分二脂不稳定,会降解为单脂;膦酸盐的化学位移在18.670×10-6至21.460×10-6之间,磷酸肌酸位于-0.380×10-6,有机多聚磷中α-P的化学位移在-8.833×10-6至-9.449×10-6之间,由于偶合作用产生P峰的裂分,P峰的偶合符合核磁中n 1的规则.结构环境影响31P的化学位移值的偏移.     

武汉东湖水体异味物质及其与水环境因子相互关系

根据2014年1—12月东湖3个湖区(水果湖、郭郑湖及汤菱湖)中9种溶解态异味物质(DMS、DMDS、DMTS、β-cyclocitral、β-ionone、MIB、GEO、IBMP和IPMP)的月间采样结果,对异味化合物浓度之间的相关性及其与东湖水体中主要环境因子的相关关系进行了分析.研究发现9种异味物质浓度整体水平在夏、秋季相对冬、春季较高,其中DMS、DMTS、β-cyclocitral、β-ionone的月平均浓度较高,且在夏季均超出嗅味阈值,其他几种异味物质浓度检出较低,对东湖的异味强度影响较小.低浓度β-cyclocitral及β-ionone具有烟草或芳香味,DMS与DMTS具有腐臭味,因此DMS及DMTS为东湖异味的主要致嗅物质.从异味物质空间分布来看,郭郑湖区的DMS、DMDS、β-cyclocitral及β-ionone年平均浓度均低于其他两个湖区,综合该湖区中相对较低的年平均总氮(TN)和叶绿素a(Chl.a)浓度以及受人类活动影响程度较低的情况,该湖区的异味问题要轻于水果湖及汤菱湖区.此外,研究发现DMTS、β-cyclocitral和β-ionone浓度与Chl.a浓度均呈显著正相关,DMDS及DMTS浓度与TN浓度呈显著正相关,DMS及β-cyclocitral浓度与溶解氧浓度呈显著负相关,表明由于大量藻类快速腐败导致的水体含氧量下降可能会对水体异味产生重要影响.为防止东湖水体恶臭的发生,对藻类进行控制尤为重要.     

巢湖表层沉积物中生物易降解物质成分特征与分布规律

富营养化湖泊的藻类残体大量沉降到湖底,其中易降解成分的降解和转化快速消耗底层水体中的溶解氧,极易造成水土界面缺氧,影响湖泊生态系统的健康.于2014年对巢湖12个样点的表层沉积物进行周年跟踪研究,分析样品中有机质来源、总有机碳(TOC)、蛋白质、总糖、总脂以及生物聚合物碳(BPC)等成分含量,揭示易降解有机质的成分特征及在巢湖的分布规律.研究表明:巢湖表层沉积物TOC含量较高,全湖样点平均含量达到1.24%.BPC含量占TOC含量的30.99%~60.48%,有机质中易降解成分含量较高,并且在冬季和夏季时在巢湖西北部湖区有明显累积;有机质及其中的生物易降解部分均主要集中在粒径4~8μm的表层沉积物上,在应用工程技术手段处理、降解表层沉积物中的过量有机质时,更应该关注粒径为4~8μm的沉积物颗粒.     

A comparative study of the hopanoid hydrocarbons in sediments of two lakes (Fuxian and Changdang) with contrasting environments

Biologically configured ββ-hopanes, geologically configured αβ-hopanes and the biogenic hopenes were determined in dated sediment cores from Lake Fuxian in SW China and Lake Changdang in Eastern China in order to investigate anthropogenic influences on the abundance, composition and provenance of hopanoid hydrocarbons in lake sediments. Based on the results, hopenes were prevalent, with maximum values reaching 148.9 μg g⁻¹ TOC in sediments of Lake Fuxian, an oligotrophic deep lake (average depth 89.6 m), where the long water column provided ample potential for the growth of hopene-producing bacteria especially the cyanobacteria. Sediment hopenes have diminished in abundance to values of 13.4–78.5 μg g⁻¹ TOC in Lake Changdang, a eutrophic shallow (average 0.8–1.2 m) body, reflecting comparatively reduced importance of nutrient level on hopene production. Historical trends in hopenes input to the sediments of each lake are strongly dependent on nutrient status. During the last few decades, human-induced eutrophication has greatly boosted bacterial production, enhancing the accumulation of hopenes in sediments. Inputs of petroleum-derived αβ-hopanes were exceptionally high (average 71.2 μg g⁻¹ TOC) in post-1968 sediments from Lake Changdang, their increase coinciding with the advent and acceleration of petroleum product use around the lake, in particular by fishing boats. Lake Fuxian on the other hand, has undergone slower economic development and the appearance of petroleum-derived αβ-hopanes in sediments was delayed to 1990 since when the average value has been 27.1 μg g⁻¹ TOC. The abundance of αβ-hopanes in Lake Changdang has created a marked decrease in the relative contribution of hopenes to total hopanoids since 1968. Conversely, the amounts of αβ-hopanes introduced to Lake Fuxian since 1990 has yet to yield a clear change in the overall proportion of hopenes, but the abundance of ββ-hopanes has declined relative to total hopanoid levels for the period.     

Organohalogen contaminants and total mercury in forage fish preyed upon by thick-billed murres in northern Hudson Bay

Twelve marine fish species collected from a thick-billed murre (Uria lomvia) breeding colony in northern Hudson Bay in the Canadian Arctic during 2007–2009 were analyzed for legacy organochlorines (e.g. PCBs, DDT), polybrominated diphenyl ethers (PBDEs), perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs), and total mercury (Hg). No one species of prey fish had the highest levels across all contaminant groups analyzed. For the two pelagic fish species sampled, concentrations of the major organochlorine groups (e.g. Σ₂₁PCB, ΣDDT, ΣCHL, ΣCBz), ΣPBDE, ΣPFCA and Hg were consistently higher in Arctic cod (Boreogadus saida) than in capelin (Mallotus villosus). Biomagnification factors from whole fish to thick-billed murre liver across all species were generally higher for Σ₂₁PCB and ΣDDT. ΣPBDE did not biomagnify.